Crystalline multinary-metal chalcogenide compositions containing only non-toxic and abundant elements are of particular interest in developing environmentally sustainable processes and devices. Copper tin sulfide (Cu2SnS3 or “CTS”) and copper zinc tin sulfide (Cu2ZnSnS4 or “CZTS”) are particularly useful examples of this class of materials, and are of interest due to their potential applications as small band-gap semiconductors, as nonlinear materials, and as suitable candidates for photovoltaic cell materials.
Thin-film photovoltaic cells typically use semiconductors such as CdTe or copper indium gallium sulfide/selenide (CIGS) as an energy absorber material. Due to toxicity of cadmium and the limited availability of indium, alternatives are sought CZTS possesses a band gap energy of about 1.5 eV and a large absorption coefficient (approx. 104 cm−1), making it a promising CIGS replacement.
Challenges in making CZTS thin-films are illustrative of the general challenges that must be surmounted in making films of crystalline multinary-metal chalcogenide compositions. Current techniques to make CZTS thin films (e.g., thermal evaporation, sputtering, hybrid sputtering, pulsed laser deposition and electron beam evaporation) require complicated equipment and therefore tend to be expensive. Electrochemical deposition is an inexpensive process, but compositional non-uniformity and/or the presence of secondary phases prevents this method from generating high-quality CZTS thin-films. CZTS thin-films can also be made by the spray pyrolysis of a solution containing metal salts, typically CuCl, ZnCl2, and SnCl4, using thiourea as the sulfur source. This method tends to yield films of poor morphology, density and grain size. Photochemical deposition has also been shown to generate p-type CZTS thin films. However, the composition of the product is not well-controlled, and it is difficult to avoid the formation of impurities such as hydroxides. The synthesis of CZTS nanoparticles, which incorporate high-boiling amines as capping agents, has also been disclosed. The presence of capping agents in the nanoparticle layer may contaminate and lower the density of the annealed CZTS film.
A hybrid solution-particle approach to CZTS involving the preparation of a hydrazine-based slurry comprising dissolved Cu—Sn chalcogenides (S or S—Se), Zn-chalcogenide particles, and excess chalcogen has been reported. However, hydrazine is a highly reactive and potentially explosive solvent that is described in the Merck Index as a “violent poison.”
Hence, there still exists a need for simple, low-cost, scalable materials and processes with a low number of operations that provide high-quality, crystalline CTS and CZTS films with tunable composition and morphology. There also exists a need for low-temperature routes to these materials using solvents and reagents with relatively low toxicity.